N-allyl phosphorothioamidates

ABSTRACT

A PHOSPHORTHIOAMIDATE HAVING THE FORMULA,   CH2=CH-CH2-NH-P(-O-R1)(=O)-S-(CH2)2-S-R2   WHEREIN R1 IS METHYL OR ETHYL, AND R2 IS AN ALKYL HAVING 1 TO 4 CARBON ATOMS, WHICH IS USEFUL AS A SYSTEMIC PESTI CIDE FOR CONTROLLING INJURIOUS PESTS, AND WHICH IS PREPARED BY THE CONDENSATION OF A THIOPHOSPHATE HAVING THE FORMULA   (CH2=CH-CH2-NH-P(-O-R1)(=O)=S).M   WHREIN R1 IS AS DEFINED ABOVE, AND M IS AN ALKALI METAL WITH A HALIDE HAVING THE FORMULA   HAL-(CH2)2-S-R2   WHEREIN R2 IS AS DEFINED ABOVE, AND HAL IS A HALOGEN.

United States Patent US. Cl. 260-948 Claims ABSTRACT OF THE DISCLOSURE A phosphorothioamidate having the formula,

wherein R is methyl or ethyl, and R is an alkyl having 1 to 4 carbon atoms, which is useful as a systemic pesticide for controlling injurious pests, and which is prepared by the condensation of a thiophosphate having the formula,

oHFoHomNH o /P :I -M R10 s wherein R is as defined above, and M is an alkali metal, with a halide having the formula,

Hal(CH g--S-R2 wherein R is as defined above, and Hal is a halogen.

This invention relates to a novel phosphorothioamidate having the Formula I,

1110/ \S'-(CHI)2R2 (I) wherein R is methyl or ethyl, and R is an alkyl having 1 to 4 carbon atoms, and a systemic pesticide containing at least one said phosphorothioamidate (I).

The phosphorothioamidate (I) can be prepared by reacting a thiophosphate having the Formula (II),

wherein R is as defined above, and M is an alkali metal, with a halide having the Formula (III),

3,786,118 Patented Jan. 15, 1974 ice Compound No. Formula 1) CH=CHCH NH 0 0.1150 s CH:CH2S 02H (2) CH2=CHCH2NH O CHaO SCHaCHaSC:HI

(3) CHFCHCHzNH 0 OHaO S-'CHflCHls CH:

(4) CH2=CHCH2NH O CHaO SCH2CH2SC4H0(H) (5) CH =CHCHNH O CzHsO S-CH2CH1SCH3 amples of the injurious insects controlled effectively by' the phosphorothioamidates (I) are, for example, planthoppers, mites, borers, scales and mealybugs, and nematodes, and other Lepidoptera, Diptera, Coleoptera, Hemiptera, and other arthropoda can be also controlled by them.

There are usually known as systemic actions either action that chemicals penetrate into tissues of plants and animals, or action that they move therein after the pene tr-ation. I is notable that the phosphorohioamidates (I) have both excellent systemic actions, and moreover have biological activities such that by use of a concentration lower than a lethal one of the phosphorothioamidates (I), a transformation of insects is caused to be disturbed and a normal propagation is prevented. Further, the phosphorothioamidates (I) have so excellent contact insecticidal effects that they can effectively control insects and mites having power of resistance to the conventional biological chemicals.

As the compounds analogous to the present Compounds I, there are known in the specifications of US. Pat. No. 3,019,250, DAS No. 1,077,215 and DAS No. 1,135,905, a phosphate having the formula, I

R 0 S (CHala-S-R:

wherein R and R are as define'd above, and A is hydrogen or an alkyl. In order to substantiate a superiority of the present compounds in insecticidal effects to the known compounds mentioned above, a test example is given as follows.

TEST EXAMPLE Into a flower pot having about 10 cm. in diameter 18 to 23 rice plants per pot were grown up to 3 to 4 leaves stage, and was sprayed thereon each 1000 fold emulsion with water of the compounds in a form of 50% emulsi compounds. The results are as shown in the following table.

illustrative but not limitative. Percent and part are by weight.

Days elapsed after the Synthesis of the Compound I spraying and lethal ra 1o percen 1 4 7 n Example 1.Into a solution of 12.0 g. of potassium Compound day days days days O-flthyl-N-allylphosphorothioamidate in 70 ml. of ethyl present com n (1) 100 613 alcohol is added 6.2 g. of ethylthioethyl chloride, and the 1 52523.? 88333333 83:33::3333313: ioi iofi oil? iii mixture is Stirred for 2 hours under refluX- The solvent NH, O 100 58.3 31' 4 21.3 1S removed by dlstillation nder a reduced pressure, and water is added to the residue. The mixture 1s extracted with chloroform. The chloroform layer is dried over an- CzHsO S --(CHr)2S---C2H5 0 hydrous sodium sulfate, and the chloroform 18 removed 4 j 77 8 63 4 71 1 15 by distillation under a reduced pressure, whereby 11.4 g.

of O-ethyl-S-(Z ethylthioethyl)-N-allyl-phosphorothioamidate is obtained as a yellow oil, N 1.5183. C2H5HN\ 0 6-7 Elementary analysis-Calculated (percent) (as /'.P\ 20 C H NO PS P, 11.50; S, 23.80; N, 5.20. Found (per- CHsO s(oH2)TS--0Hs cent) P, 10.97; S, 23.88; N, 5.09. The compound disclosed in Example 12 of mar. No. 3,019,250. p e 2-Acc0rding to the procedure similar to that The compound disclosed in Example 28 of the said U.S.P. "The compound disclosed in D.A.S.No.1,077,215. of Example 1, the following compounds are obtained.

Compound obtained Elementary analysis Calcd Found Ex. Reflective No. Thiophosphate Halide Phosphorothioamidate index Formula P S N P S N 2 Potassium O-methyl-N- Ethylthio- O-methyl-S-(iZ-ethylthio- No 1.5215 C HmNO PS 12.13 11.25 5. 49 12.00 24.95 5. 2

allylphosphorothioethylethyl)-N-allylphosamidate. chloride. phrothioamidate. 3 --do 2-rnethyl- O-methyl-S-(2-methyl- Nn 1.5301 C'IHNNOZPSI 12. 84 26.57 5.80 12. 74 26.71 5.52

thioethyl thioethyD-N-allylphoschloride. phorothioamidate. 4 Potassium O-ethyl-N- o 0-ethyl-S-(2-methylthio- Ne 1. 5244 CaHioNOzPSn 12.13 25.11 5. 49 11.77 25.42 5. 37 allylphosphorothioethyD-N-allylphosamidatc. pherothioamidate.

The present Compounds I may be used as it is without addition of other components, and may be combined with a carrier in order to form preparations which are handled easily in a practical use. According to the procedure well known by the skilled in the art, the present Compounds I may be optionally formulated into emulsifiable concentrates, wettable powders, oil sprays, dusts, aerosols, heating fumigants, fine granules, granules or the like. If desired, the present Compounds I may be combined with one or more of other active ingredients and fertilizers in order to widen and enhance the elfects thereof.

For example, multi-purpose preparations may be prepared by thecombination with the other organic phosphorus insecticides such as Sumithion (a trademark of Sumitomo Chemical Co., in Japan) and Dimetoate, pyrethroid insecticides such as allethrin and pyrethrin, organic chlorine insecticides such as BHC and DDT, carbamate insecticides such as 3,4 dimethylphenyl-N-methylcarbamate, 2- sec.-butylphenyl-N-methylcarbamate, S-methylphenyl-N-methylcarbamate and l-naphthyl-N-methylcarbamate, synergists, repellents, attractants and other analogues, and as the results thereof, a certain synergistic effect may be expected.

The present invention will be illustrated in more detail with reference to the following examples, which are only Preparation of the pesticidal composition Active ingredient Solvent Emulsifier (percent) (percent) (percent) Compound (1), 50-. Xylol Sorpol-2020, 20. Compound (5), 20 Oyclohexanone, 50..-- Sorpol-2539, 30.

* Sol-pol is a trademark of Toho Chem. Co., in Japan.

Example 6: Wettable powder.-Into 55 parts of 200 mesh talc, is added dropwise a mixture of parts of the Compound 4 and an emulsifier (Sorpol-2492: a trademark of Toho Chem. Co., in Japan), while being stirred well in a mixer, whereby a wettable powder is obtained. In a practical use, the powder is diluted with water.

Example 7: Granule-Each compound, a binder and a diluent mentioned in the following table are well mixed in this order, and the mixture is mixed with a small amount of water, granulated by means of a gr-anulator and dried, whereby each granule is obtained.

In a practical use, the granule is spread as it is.

Active ingredient Diluent (percent) Binder (percent) (percent) Compound (1), 2-.- Sodium ligninsulfonate, l. Clay, 97. Compound (2), Sodium ligninsulionate, 2... Clay, 93.

Example 8: Dust.--In a mixing ratio mentioned below, a solution of each compound in a small amount of acetone is well mixed with 200 mesh talc, and thereafter evaporation of acetone gives each dust. In a practical use, the dust is spread as it is.

Active ingredient Diluent (percent) (percent) Compound (3), 2 Talc, 98. Compound (4), 4 Talc, 96.

The following test examples are given in order to sub stantiate a pesticidal effect of the present compound on insects and fungi.

Test Example 1: Lethal effect on carmine mite (Tetranychus telarius).-Many of carmine mites were made parasitic on mottled kidney beans at a 2 leaves stage days after the sowing. Into each aqueous dilution,

of the present compounds in a form of a wettable powder, were dipped leaves of the bean, on which the mites were parasitic, for one minute, and were given water in order not to be died. After 48 hours, the death and alive were observed microscopically to calculate LC (medium lethal concentration). The results are as shown in the following table.

Compound No.: LC (dilution times) Days elapsed and lethal ratio (percent) Test Example 4: Effect on smaller brown planthoppers in the soil treatment.Each 6% granules of the present compounds was spread in a ratio of 6 kg./1O ares near the root of rice plants grown at the tillering stage in an 1/1000,-000 Wagncrs pot, and adults of the plant hoppers were released according to the lapse of days and covered with a wire cage. After 24 hours, the death and alive were recorded. The results are as shown in the following table.

Days elapsed and lethal ratio (percent) After After After After After Compound No. 1 day 4 days 7 days 11 days 15 days Test Example 5: Effect on green peach aphids (Myzus persicae) in the soil treatment.-Many of the aphids were made parasitic on Chinese cabbages grown in a pot one month after the sowing, and each 5% granules of the present compounds was spread at a rate of 6 kg./l0 ares near the root thereof. After 3 days, the death and alive were recorded to calculate the lethal ratio. The results are as shown in the following table.

Compound No.: Lethal ratio (percent) (1) 100 (2) 100 (3 100 Dimetoate 100 Test Example 6: Residual effect on two-spotted spider mites (Tetranychus urticae).Each 3% dust of the present compounds was spread in a ratio of 3 -kg./ 10 ares on mottled kidney beans at a 2 leaves stage in a flower pot 20 days after the sowing by means of a bell jar duster, and according to the lapse of days, adults of the mites were made parasitic thereon. After 48 hours, the lethal ratio was calculated. The results are as shown in the following table.

Days elapsed and lethal ratio (percent) After After After After Compound No. 1 day 3 days 7 days 12 days After After After After After Compound No. 1 day 4 days 7 days 11 days 16 days Test Example 3: Lethal effect on smaller brown planthoppers (Laodelphax striatellus). Rice plants (15 cm. to 20 cm. tall) which had elapsed 15 days after germination were dipped into each aqueous dilution of the present compounds in a form of emulsifiable concentrates, for one minute, and after air-drying, were placed into a glass tube. Thereafter, 20 to 30 planthoppers were released therein, and covered with a wire net. After 24 hours, the death and alive were recorded to calculate LC The results are as shown in the following table.

Compound No.: LC (dilution times) Test Example 7: Effect on various tortrixes and aphids. In an apple tree garden which has been damaged by the tortrixes and aphids, each 5% granules of the present compounds was spread 1 cm.-radius-circlewise in a ratio of 7 g./tree near the root of a 5 years old apple tree. The follovw'ng results were obtained 5 days after the spreading.

Number of the parasite Number of the alive before spreading per parasite per 500 leaves leaves after 5 days Compound No. Tortrixes Aphids 'Iortrixes Aphids Test Example 8: Controlling effect on powdery mildew (Sphaerotheca fuliginea).Cucumbers (variety: Aonagafushinari) were grown up to a 3 to 4 leaves stage in a 9 cm. flower pot.

Each wettable powder of the present compounds was diluted with water to adjust the concentration of the active ingredient to 1000 p.p.m., and each 10 ml. per pot of the dilution was sprayed. Spore suspension of the powdery mildew was inoculated thereinto by spraying one day thereafter. i

The degree of disease concerning upper 4 leaves was observed after 10 days and percentage of contraction was calculated from a spotted area. As is clear from the results shown in the following table, the present compounds stand comparison with a commercially available chemical 1D the controlling eifects.

Concentration Average of the active Number percentage in redient of leaves p.p.m.) tested contraction 1, 000 40 8. 1 1,000 40 4.4 1,000 40 4.7 1,000 40 5.1 1,000 40 9.3 2-(1-methylheptyl)-4,6 1, 000 ,40 4. 2

phenyl crotonate N on-treatment 40 54. 1

A commercially available fungicide as Karathane.

Test Example 9: Controlling elfect on rice blast (Pyricularia 0ryzae).--On rice plants grown up to a 4 leaves stage in a 9 cm. flower pot, was sprayed each emulsifiable concentrate of the present compounds in a ratio of 10 ml./pot by means of a spray gun. After 24 hours, the spore suspension of rice blast (Pyricularia oryzae) cultured in an oatmeal medium was inoculated by spraying. The number of spots produced on a top of the leaf was counted to know the controlling effect. As is clear from the results shown in the following table, the present compounds stand comparison with a commercially available chemical in the controlling effect.

Concentration of the active Number Number ingredient of leaves of spots (p.p.m.) tested per leaf Compound No.:

(1) 500 15 6. 5 (2) 500 15 6. 9 (3) 500 15 8. 3 (4) 500 6. 7 (5) 500 15 10. 8 0,0-Diisopropyl-S-benzylphosphorothioate 500 15 6. l Non-treatment. 15 83. 8

1 A commercially available fungicide as Kitazin P.

What is claimed is: 1. A compound of the formula,

CHz=CHCHzNH O P RIO/ z)2 2 wherein R is methyl or ethyl, and R is an alkyl having 1 to 4 carbon atoms.

2. A compound of claim 1, wherein R is methyl. 3. A compound of claim 1, wherein R is ethyl. 4. A compound of claim 1, wherein R is methyl. 5. A compound of claim 1, wherein R is ethyl. 6. A compound of claim 1, wherein R is methyl and R is methyl.

' 7. A compound of claim 1, wherein R is methyl and R is ethyl.

8. A compound of claim 1, wherein R is methyl and R is n-butyl.

9. A compound of claim 1, wherein R is ethyl and R is methyl.

10. A compound of claim 1, wherein R is ethyl and R vis ethyl.

' References Cited UNITED STATES PATENTS l/1962 Kayser et al 260959 X 6/1972 Tsuchiya et a1. 260-959 X LEWIS GOTTS, Primary Examiner R. L. RAYMOND,'Assistant Examiner 

